An Antiaromatic Electrode‐Active Material Enabling High Capacity and Stable Performance of Rechargeable Batteries

Shin, Ji‐Young; Yamada, Tetsuya; Yoshikawa, Hideki; Awaga, Kunio; Shinokubo, Hiroshi

doi:10.1002/anie.201310374

Cited by 174 publications

(122 citation statements)

References 27 publications

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“…The first electrochemical reduction, attributable to a reaction from Ni(nor) to Ni(nor) ·− (ref. 21), appeared at −0.65 V versus Ag/AgCl (Supplementary Note 10). Subsequent electrochemical single-molecule conductance experiments brought the LUMO-mediated transport channel closer to the electrode potential as the electrochemical potential was changed from +0.45 to −0.30 V versus Ag/AgCl.…”

Section: Resultsmentioning

confidence: 99%

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Highly-conducting molecular circuits based on antiaromaticity

et al. 2017

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Aromaticity is a fundamental concept in chemistry. It is described by Hückel’s rule that states that a cyclic planar π-system is aromatic when it shares 4n+2 π-electrons and antiaromatic when it possesses 4n π-electrons. Antiaromatic compounds are predicted to exhibit remarkable charge transport properties and high redox activities. However, it has so far only been possible to measure compounds with reduced aromaticity but not antiaromatic species due to their energetic instability. Here, we address these issues by investigating the single-molecule charge transport properties of a genuinely antiaromatic compound, showing that antiaromaticity results in an order of magnitude increase in conductance compared with the aromatic counterpart. Single-molecule current–voltage measurements and ab initio transport calculations reveal that this results from a reduced energy gap and a frontier molecular resonance closer to the Fermi level in the antiaromatic species. The conductance of the antiaromatic complex is further modulated electrochemically, demonstrating its potential as a high-conductance transistor.

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Section: Resultsmentioning

confidence: 99%

“…1). Ni(nor) features a chemically stable, structurally rigid antiaromatic porphyrinoid moiety202122 where antiaromaticity can be preserved due in no small part to its molecular rigidity. The electronic properties of Ni(nor) are benchmarked against a porphyrin-based aromatic counterpart, Ni(porph) (Fig.…”

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Highly-conducting molecular circuits based on antiaromaticity

et al. 2017

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“…Among the tetrapyrrolic systems (Scheme ), that is, porphyrins (Por) and corroles (Corr), the delocalization results in the aromatic character of the macrocycle, which is in line with the 4 n +2 Hückel rule and the presence of eighteen π electrons in the macrocyclic conjugation circuit. In norcorrole (NCR), a recently discovered tetrapyrrole, the conjugation path involves sixteen π electrons, and thus, the system becomes antiaromatic . To some extent, the reactivity of the macrocycle and some other properties, for example, the redox behavior of norcorrole in its nickel(II) complex (NCRNi, 1 ) resemble those of aromatic systems.…”

Section: Introductionmentioning

confidence: 99%

Nitration of Norcorrolatonickel(II): First Observation of a Diatropic Current in a System Comprising a Norcorrole Ring

Deng

Stępień

et al. 2016

Chemistry A European J

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A one-pot reaction of 5,14-bis(mesityl)-norcorrolatonickel(II) with isoamyl nitrite under mild reaction conditions resulted in the consecutive formation of 3-nitro-, 3,12-dinitro- and 3,16-dinitro-, 3,7,12-trinitro-, and 3,7,12,16-tetranitro-norcorrolatonickel(II) in 50-80% yield. The substituted macrocycles retained their antiaromatic character. The observed regioselectivity of the substitution was analyzed by comparing the relative energies of the DFT energy-optimized models of the radical or arenium cationic intermediates that can be formed upon reaction with NO2. The nitrated systems were characterized by high-resolution mass spectrometry, NMR and UV/Vis spectroscopy, X-ray diffraction analysis, cyclic voltammetry, and DFT calculations. A significant and systematic cathodic shift of the redox couples was observed to correlate with an increasing number of the NO2 group. A decrease of the LUMO energies in the tri- and tetra-nitrated products stabilizes mono- and bis-reduced complexes of these ligands. The reduction takes place on the macrocycle rather than on the metal ion leading to the consecutive formation of stable paramagnetic monoanion radicals and water-soluble diamagnetic dianions with an aromatic character, which were revealed by ESR and (1)H NMR measurements, respectively. The electronic structures of the reduced forms were analyzed by extensive TD-DFT calculations.

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“…NiNC displays to be antiaromatic because of its highly planar structure and the presence of 16 π electrons along the conjugation circuit. Only Shin et al reported the practical application of the antiaromatic NiNC as an electrode-active material in a Li metal free rechargeable battery [15]. It showed that NiNC had the bipolar redox property [14,15].…”

Section: Introductionmentioning

confidence: 98%

A glassy carbon electrode modified with a nickel(II) norcorrole complex and carbon nanotubes for simultaneous or individual determination of ascorbic acid, dopamine, and uric acid

Deng

Huang

2016

Microchim Acta

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The authors report on the synthesis of a hybrid material consisting of the porphyrinoid metal complex nickel(II) norcorrole that was noncovalently bound to carbon nanotubes (CNT-NiNC). The hybrid was characterized by UV-vis, FTIR spectroscopy, and thermogravimetric analysis. The CNTNiNC hybrid possesses high catalytic activity and selectivity toward the oxidation of ascorbic acid, dopamine, and uric acid. It was used to modify a glassy carbon electrode which then is shown to enable simultaneous or individual determination of ascorbic acid (AA), dopamine (DA), and uric acid (UA) at pH 6.5 and typical working potentials of −70, 200 and 380 mV (vs. SCE). The detection limits (at an SNR of 3) are 2.0 μM for AA, 0.1 μM for DA, and 0.4 μM for UA.

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An Antiaromatic Electrode‐Active Material Enabling High Capacity and Stable Performance of Rechargeable Batteries

Cited by 174 publications

References 27 publications

Highly-conducting molecular circuits based on antiaromaticity

Highly-conducting molecular circuits based on antiaromaticity

Nitration of Norcorrolatonickel(II): First Observation of a Diatropic Current in a System Comprising a Norcorrole Ring

A glassy carbon electrode modified with a nickel(II) norcorrole complex and carbon nanotubes for simultaneous or individual determination of ascorbic acid, dopamine, and uric acid

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